|Publication number||US7749621 B2|
|Application number||US 11/493,414|
|Publication date||Jul 6, 2010|
|Filing date||Jul 26, 2006|
|Priority date||Mar 14, 1997|
|Also published as||CA2452637A1, CA2452637C, CN1541196A, CN1541196B, DE60223375D1, DE60223375T2, EP1406847A1, EP1406847B1, US7096692, US8012610, US20030027000, US20060263610, US20100233473, WO2003006393A1|
|Publication number||11493414, 493414, US 7749621 B2, US 7749621B2, US-B2-7749621, US7749621 B2, US7749621B2|
|Inventors||Charles B. Greenberg, Janos Szanyi|
|Original Assignee||Ppg Industries Ohio, Inc.|
|Export Citation||BiBTeX, EndNote, RefMan|
|Patent Citations (175), Non-Patent Citations (80), Referenced by (5), Classifications (47), Legal Events (3)|
|External Links: USPTO, USPTO Assignment, Espacenet|
This application is a divisional of U.S. application Ser. No. 10/193,446, filed Jul. 11, 2002 now U.S. Pat. No. 7,096,692, which is a continuation-in-part of U.S. application Ser. No. 10/075,316 to Greenberg et al., entitled “Photocatalytically-Activated Self-Cleaning Appliances”, filed Feb. 14, 2002 now U.S. Pat. No. 6,722,159, which is a divisional of U.S. application Ser. No. 09/282,943 filed Apr. 1, 1999 (now U.S. Pat. No. 6,413,581), which is a divisional of U.S. application Ser. No. 08/899,257, filed Jul. 23, 1997 (now U.S. Pat. No. 6,027,766), which claimed the benefit of U.S. Provisional Application Ser. No. 60/040,566, filed Mar. 14, 1997, all of which applications are herein incorporated by reference in their entirety. This application also claims the benefit of U.S. Provisional Application Ser. No. 60/305,057 filed Jul. 13, 2001, which is herein incorporated by reference in its entirety.
The present invention relates to methods of depositing photoactive coatings on a substrate (e.g., a glass sheet or a continuous float glass ribbon), to methods of making photocatalytic and/or hydrophilic coatings that exhibit photoactivity upon irradiation with visible light, and to articles of manufacture prepared according to the methods.
For many substrates, e.g., glass substrates such as architectural windows, automotive transparencies, and aircraft windows, it is desirable for good visibility that the surface of the substrate is substantially free of surface contaminants, such as common organic and inorganic surface contaminants, for as long a duration as possible. Traditionally, this has meant that these surfaces are cleaned frequently. This cleaning operation is typically performed by manually wiping the surface with or without the aid of chemical cleaning solutions. This approach can be labor, time, and/or cost intensive. Therefore, a need exists for substrates, particularly glass substrates, having surfaces that are easier to clean than existing glass substrates and which reduce the need or frequency for such manual cleaning.
It is known that some semiconductor metal oxides can provide a photoactive (hereinafter “PA”) coating. The terms “photoactive” or “photoactively” refer to the photogeneration of a hole-electron pair when illuminated by radiation of a particular frequency, usually ultraviolet (“UV”) light. Above a certain minimum thickness, these PA coatings are typically photocatalytic (hereinafter “PC”). By “photocatalytic” is meant a coating having self-cleaning properties, i.e., a coating which upon exposure to certain electromagnetic radiation, such as UV, interacts with organic contaminants on the coating surface to degrade or decompose the organic contaminants. In addition to their self-cleaning properties, these PC coatings are also typically hydrophilic, i.e. water wetting with a contact angle with water of generally less than 20 degrees. The hydrophilicity of the PC coatings helps reduce fogging, i.e. the accumulation of water droplets on the coating, which fogging can decrease visible light transmission and visibility through the coated substrate.
A problem with these conventional PC coatings is that they typically exhibit photoactivity or photocatalysis only upon exposure to ultraviolet (UV) light in wavelengths shorter than about 380 nanometers (nm). This means that the PC coatings make use of only about 3% to 5% of the solar energy that reaches the earth, which can necessitate the use of a UV light source (such as a conventional mercury or black lamp) in order to provide sufficient energy for photocatalysis.
In order to address this problem, attempts have been made to modify conventional PC coatings to shift the photoabsorption band of the coating material from the UV region into the visible region (400 nm to 800 nm) of the electromagnetic spectrum. For example, U.S. Pat. No. 6,077,492 to Anpo et al. discloses a method of shifting the photoabsorption band of titanium oxide photocatalysts from the UV region into the visible light region by high-energy ion implantation of selected metal ions into the photocatalyst. Subsequent investigation of this ion implantation method has determined that the photoabsorption band shift into the visible region requires not only high-energy ion implantation but also calcination in oxygen of the metal ion-implanted titanium oxide (Use Of Visible Light. Second-Generation Titanium Oxide Photocatalysts Prepared By The Application Of An Advanced Metal Ion-Implantation Method, M. Anpo, Pure Appl. Chem., Vol. 72, No. 9, pp. 1787-1792 (2000)). EP 1,066,878 discloses a sol-gel method of doping titania with minute amounts of selected metal ions to shift the photoabsorption band of the titania into the visible region.
However, these ion implantation and sol-gel coating methods are not economically or practically compatible with certain application conditions or substrates. For example, in a conventional float glass process, the float glass ribbon in the molten metal bath can be too hot to accept the sol due to evaporation or chemical reaction of the solvent used in the sol. Conversely, when the sol is applied to substrates that are below a specific temperature for the formation of crystalline forms of the catalyst, the sol-coated substrates are reheated. Reheating to a temperature sufficient to calcinate the coating or form the crystallized photocatalyst can require a substantial investment in equipment, energy, and handling costs, and can significantly decrease production efficiency. Further, reheating a sodium containing substrate, such as soda-lime-silica glass, to a temperature sufficient to calcinate the coating increases the opportunity for sodium ions in the substrate to migrate into the coating. This migration can result in what is conventionally referred to as “sodium ion poisoning” of the deposited coating. The presence of these sodium ions can reduce or destroy the photocatalytic activity of the PC coating. Moreover, the ion-implantation and sol-gel methods typically result in thick coatings, e.g., several microns thick, which may have an adverse effect on the optical and/or aesthetic properties of coated articles.
Typically, as the thickness of the PC coating increases, the light transmittance and the reflectance of the coating go through a series of minimums and maximums due to optical interference effects. The reflected and transmitted color of the coating also varies due to these optical effects. Thus, coatings thick enough to provide the desired self-cleaning properties can have undesirable optical characteristics.
Therefore, it would be advantageous to provide a method of making a PA coating with photoabsorption in the visible region that is compatible with a conventional float glass process and/or an article made in accordance with the method which reduce or eliminate at least some of the above-described drawbacks.
A method is provided for forming a coating by depositing a precursor composition over at least a portion of a substrate surface by a CVD coating device. The precursor composition includes a photoactive coating precursor material, such as a metal oxide or semiconductor metal oxide precursor material, and a photoabsorption band modifying precursor material. In one embodiment, the coating is deposited over a float glass ribbon in a molten metal bath. In another embodiment, the coating is deposited over a float glass ribbon after exiting the molten metal bath but prior to entering a heat treatment device, such as an annealing lehr. The resultant coating is one that results in at least hydrophilicity, e.g., photoactive hydrophilicity, of a coating on a substrate and can also result in photocatalytic activity sufficient to be a photocatalytic coating.
Another method of forming a photoactive coating having a photoabsorption band in the visible region of the electromagnetic spectrum includes depositing a precursor composition over at least a portion of a float glass ribbon in a molten metal bath by a CVD coating device. The precursor composition includes at least one titania precursor material. In one embodiment, the titania precursor material includes titanium and oxygen, e.g., an alkoxide, such as but not limited to titanium methoxides, ethoxides, propoxides, butoxides, and the like or isomers thereof, such as but not limited to titanium isopropoxide, tetraethoxide, and the like. In another embodiment, the titania precursor material comprises titanium tetrachloride. The precursor composition also includes at least one other precursor material having a metal selected from chromium (Cr), vanadium (V), manganese (Mn), copper (Cu), iron (Fe), magnesium (Mg), scandium (Sc), yttrium (Y), niobium (Nb), molybdenum (Mo), ruthenium (Ru), tungsten (W), silver (Ag), lead (Pb), nickel (Ni), rhenium (Re), or any mixtures or combinations containing one or more thereof. In one embodiment, the other precursor material can be an oxide, alkoxide, or mixtures thereof. All root mean square roughness values are those determinable by atomic force microscopy by measurement of the root mean square (RMS) roughness over a surface area of one square micrometer. Additionally, any reference “incorporated herein” is to be understood as being incorporated in its entirety.
An additional method of the invention includes depositing a sodium ion diffusion barrier layer over at least a portion of a substrate, depositing a photoactive coating over the barrier layer, and implanting one or more selected metal ions into the photoactive coating by ion-implantation to form a photoactive coating having an absorption band including at least one wavelength in the range of 400 nm to 800 nm.
An article of the invention includes a substrate having at least one surface and a coating deposited over at least a portion of the substrate surface. The coating includes a photoactive coating material, such as titania, and at least one additional material selected from chromium (Cr), vanadium (V), manganese (Mn), copper (Cu), iron (Fe), magnesium (Mg), scandium (Sc), yttrium (Y), niobium (Nb), molybdenum (Mo), ruthenium (Ru), tungsten (W), silver (Ag), lead (Pb), nickel (Ni), rhenium (Re), or any mixtures or combinations containing one or more thereof. In one embodiment, the coating is deposited over the substrate by chemical vapor deposition.
As used herein, spatial or directional terms, such as “inner”, “outer”, “above”, “below”, “top”, “bottom”, and the like, relate to the invention as it is shown in the drawing figures. However, it is to be understood that the invention can assume various alternative orientations and, accordingly, such terms are not to be considered as limiting. Further, all numbers expressing dimensions, physical characteristics, processing parameters, quantities of ingredients, reaction conditions, and the like used in the specification and claims are to be understood as being modified in all instances by the term “about”. Accordingly, unless indicated to the contrary, the numerical values set forth in the following specification and claims are approximations that can vary depending upon the desired properties sought to be obtained by the present invention. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical value should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques. Moreover, all ranges disclosed herein are to be understood to encompass any and all subranges subsumed therein. For example, a stated range of “1 to 10” should be considered to include any and all subranges between (and inclusive of) the minimum value of 1 and the maximum value of 10; that is, all subranges beginning with a minimum value of 1 or more and ending with a maximum value of 10 or less, e.g., 5.5 to 10. Further, as used herein, the terms “deposited over” or “provided over” mean deposited or provided on but not necessarily in surface contact with. For example, a coating “deposited over” a substrate does not preclude the presence of one or more other coating films of the same or different composition located between the deposited coating and the substrate. Additionally, all percentages disclosed herein are “by weight” unless indicated to the contrary. All root mean square roughness values are those determinable by atomic force microscopy by measurement of the root mean square (RMS) roughness over a surface area of one square micrometer. Additionally, all references “incorporated by reference” herein are to be understood as being incorporated in their entirety.
Referring now to
A photoactively-modified (hereinafter “PM”) coating 24 of the invention can be deposited over at least a portion of the substrate 22, e.g., over all or a portion of a major surface of the substrate 22, such as over all or a portion of the surface 21 or the surface 60. In the illustrated embodiment, the PM coating 24 is shown on the surface 21. As used herein, the term “photoactively modified” refers to a material or coating which is photoactive and which includes at least one additive or dopant that acts to shift and/or widen the photoabsorption band of the material compared to that of the material without the additive. By “photoabsorption band” is meant the range of electromagnetic radiation absorbed by a material to render the material photoactive. The PM coating 24 can be photocatalytic, photoactively hydrophilic, or both. By “photoactively hydrophilic” is meant a coating in which the contact angle of a water droplet on the coating decreases with time as a result of exposure of the coating to electromagnetic radiation in the photoabsorption band of the material. For example, the contact angle can decrease to a value less than 15°, such as less than 10°, and can become superhydrophilic, e.g., decrease to less than 5°, after sixty minutes of exposure to radiation in the photoabsorption band of the material having an intensity of 24 W/m2 at the PM coating surface. Although photoactive, the coating 24 may not necessarily be photocatalytic to the extent that it is self-cleaning, i.e., may not be sufficiently photocatalytic to decompose organic material like grime on the coating surface in a reasonable or economically useful period of time.
The PM coating 24 of the invention includes (1) a photoactive coating material and (2) an additive or dopant configured to widen or shift the photoabsorption band of the coating compared to that of the coating without the dopant material. The photoactive coating material (1) includes at least one metal oxide, such as but not limited to, one or more metal oxides or semiconductor metal oxides, such as titanium oxides, silicon oxides, aluminum oxides, iron oxides, silver oxides, cobalt oxides, chromium oxides, copper oxides, tungsten oxides, zinc oxides, zinc/tin oxides, strontium titanate, and mixtures thereof. The metal oxide can include oxides, super-oxides or sub-oxides of the metal. The metal oxide can be crystalline or at least partially crystalline. In one exemplary coating of the invention, the photoactive coating material is titanium dioxide. Titanium dioxide exists in an amorphous form and three crystalline forms, i.e., the anatase, rutile and brookite crystalline forms. The anatase phase titanium dioxide is particularly useful because it exhibits strong photoactivity while also possessing excellent resistance to chemical attack and excellent physical durability. However, the rutile phase or combinations of the anatase and/or rutile phases with the brookite and/or amorphous phases are also acceptable for the present invention.
The photoabsorption band widening or shifting material (2) can be any material that widens or shifts the photoabsorption band of the resultant coating to extend at least partly into, or extend further into, the visible region of the spectrum (i.e., widens or shifts the photoabsorption band to include at least one wavelength in the range of 400 nm to 800 nm not in the photoabsorption band of the coating without the dopant material (2)). In one exemplary embodiment, the material (2) includes at least one of chromium (Cr), vanadium (V), manganese (Mn), copper (Cu), iron (Fe), magnesium (Mg), scandium (Sc), yttrium (Y), niobium (Nb), molybdenum (Mo), ruthenium (Ru), tungsten (W), silver (Ag), lead (Pb), nickel (Ni), rhenium (Re), or any mixtures or combinations containing any one or more thereof. The material (2) is present in the PM coating 24 in an amount sufficient to widen or shift the photoabsorption band of the coating 24 to extend at least partly into, or extend further into, the visible region without adversely impacting the desired coating performance, e.g., reflectivity, transmittance, color, etc. Additionally, in the practice of the invention, the material (2) does not necessarily have to be concentrated at or near the coating surface 21 but, rather, can be deposited in such a manner that it is dispersed or incorporated into the bulk of the coating 24.
The PM coating 24 should be sufficiently thick so as to provide an acceptable level of photoactivity, e.g., photocatalytic activity and/or photoactive hydrophilicity, for a desired purpose. There is no absolute value which renders the PM coating 24 “acceptable” or “unacceptable” because whether a PM coating 24 has an acceptable level of photoactivity varies depending largely on the purpose and conditions under which the PM coated article is being used and the performance standards selected to match that purpose. However, the thickness of the PM coating 24 to achieve photoactive hydrophilicity can be much less than is needed to achieve a commercially acceptable level of photocatalytic self-cleaning activity. For example, in one embodiment the PM coating 24 can have a thickness in the range of 10 Å to 5000 Å, where thicker coatings in this range can have photocatalytic self-cleaning activity for at least some period of time as well as hydrophilicity. As the coatings get thinner in this range, photocatalytic self-cleaning activity typically decreases in relation to performance and/or duration. As coating thickness decreases in such ranges as 50 Å to 3000 Å, e.g., 100 Å to 1000 Å, e.g., 200 Å to 600 Å, e.g., 200 Å to 300 Å, photocatalytic self-cleaning activity may be immeasurable but photoactive hydrophilicity can still be present in the presence of selected electromagnetic radiation, e.g., within the photoabsorption band of the material.
In another aspect of the invention, the outer surface 25 of the PM coating 24 of the invention can be much smoother than previous self-cleaning coatings while still maintaining its photoactive hydrophilicity and/or photocatalytic activity. For example, the PM coating 24, in particular the top or outer surface 25 of the coating, can have an RMS surface roughness of less than 5 nm even for thin coatings in the above ranges, such as 200 Å to 300 Å, e.g., less than 4.9 nm, e.g., less than 4 nm, e.g., less than 3 nm, e.g., less than 2 nm, e.g., less than 1 nm e.g., 0.3 nm to 0.7 nm.
In a still further aspect of the invention, the PM coating 24 can be made denser than previous hydrophilic, self-cleaning coatings. For example, the PM coating 24 can be substantially non-porous. By “substantially non-porous” is meant that the coating is sufficiently dense that the coating can withstand a conventional hydrofluoric acid test in which a drop of 0.5 weight percent (wt. %) aqueous hydrofluoric acid (HF) solution is placed on the coating and covered with a watch glass for 8 minutes (mins) at room temperature. The HF is then rinsed off and the coating visually examined for damage. An alternative HF immersion test is described in Industrial Engineering Chemistry & Research, Vol. 40, No. 1, page 26, 2001 by Charles Greenberg, herein incorporated by reference. The denser PM coating 24 of the invention provides more protection to the underlying substrate against chemical attack than previous more porous self-cleaning coatings and also is harder and more scratch resistant than previous sol-gel applied self-cleaning coatings.
The PM coating 24 can be deposited directly on, i.e., in surface contact with, the surface 21 of the substrate 22 as shown in
Alternatively, one or more other layers or coatings can be interposed between the PM coating 24 and the substrate 22. For example, the PM coating 24 can be an outer or the outermost layer of a multilayer stack of coatings present on substrate 22 or the PM coating 24 can be embedded as one of the layers other than the outermost layer within such a multi-layer stack. By “an outer layer” is meant a layer receiving sufficient exciting electromagnetic radiation, e.g., radiation within the photoabsorption band of the layer material, to provide the coating with sufficient photoactivity to be at least photoactively hydrophilic if not necessarily photocatalytic. In one embodiment, the PM coating 24 is the outermost coating on the substrate 22.
A PM coating 24 of the invention can be formed on the substrate 22 by any conventional method, such as ion-implantation, spray pyrolysis, chemical vapor deposition (CVD), or magnetron sputtered vacuum deposition (MSVD). In the ion-implantation method, metal ions are implanted into the coating by high voltage acceleration. In the spray pyrolysis method, an organic or metal-containing precursor composition having (1) a metal oxide precursor material, e.g., a titania precursor material, and (2) at least one photoabsorption band modifying precursor material, i.e., a dopant material (such as an organometallic precursor material), is carried in an aqueous suspension, e.g. an aqueous solution, and is directed toward the surface of the substrate 22 while the substrate 22 is at a temperature high enough to cause the precursor composition to decompose and to form a PM coating 24 on the substrate 22. In a CVD method, the precursor composition is carried in a carrier gas, e.g., nitrogen gas, and directed toward the substrate 22. In the MSVD method, one or more metal-containing cathode targets are sputtered under reduced pressure in an inert or oxygen-containing atmosphere to deposit a sputter coating over substrate 22. The substrate 22 can be heated during or after coating to cause crystallization of the sputter coating to form the PM coating 24. For example, one cathode can be sputtered to provide the metal oxide precursor material (1) and another cathode can be sputtered to provide the dopant material (2). Alternatively, a single cathode already doped with the desired dopant material can be sputtered to form the PM coating 24.
Each of the methods has advantages and limitations depending upon the desired characteristics of the PM coating 24 and the type of glass fabrication process. For example, in a conventional float glass process molten glass is poured onto a pool of molten metal, e.g., tin, in a molten metal (tin) bath to form a continuous float glass ribbon. Temperatures of the float glass ribbon in the tin bath generally range from 1203° C. (2200° F.) at the delivery end of the bath to 592° C. (1100° F.) at the exit end of the bath. The float glass ribbon is removed from the tin bath and annealed, i.e. controllably cooled, in a lehr before being cut into glass sheets of desired length and width. The temperature of the float glass ribbon between the tin bath and the annealing lehr is generally in the range of 480° C. (896° F.) to 580° C. (1076° F.) and the temperature of the float glass ribbon in the annealing lehr generally ranges from 204° C. (400° F.) to 557° C. (1035° F.) peak. U.S. Pat. Nos. 4,466,562 and 4,671,155 (hereby incorporated by reference) provide a discussion of the float glass process.
The CVD and spray pyrolysis methods may be preferred over the MSVD method in a float glass process because they are more compatible with coating continuous substrates, such as float glass ribbons, at elevated temperatures. Exemplary CVD and spray pyrolysis coating methods are described in U.S. Pat. Nos. 4,344,986; 4,393,095; 4,400,412; 4,719,126; 4,853,257; and 4,971,843, which patents are hereby incorporated by reference.
In the practice of the invention, one or more CVD coating apparatus can be employed at several points in the float glass ribbon manufacturing process. For example, CVD coating apparatus may be employed as the float glass ribbon travels through the tin bath, after it exits the tin bath, before it enters the annealing lehr, as it travels through the annealing lehr, or after it exits the annealing lehr. Because the CVD method can coat a moving float glass ribbon yet withstand the harsh environments associated with manufacturing the float glass ribbon, the CVD method is particularly well suited to provide the PM coating 24 on the float glass ribbon in the molten tin bath. U.S. Pat. Nos. 4,853,257; 4,971,843; 5,536,718; 5,464,657; 5,714,199; and 5,599,387, hereby incorporated by reference, describe CVD coating apparatus and methods that can be used in the practice of the invention to coat a float glass ribbon in a molten tin bath.
For example, as shown in
Exemplary coating precursor materials (1) (e.g., titania precursor materials) that can be used in the practice of the present invention to form titanium dioxide PM coatings 24 by the CVD method include, but are not limited to, oxides, sub-oxides, or super-oxides of titanium. In one embodiment, the precursor material (1) can include one or more titanium alkoxides, such as but not limited to titanium methoxide, ethoxide, propoxide, butoxide, and the like; or isomers thereof, e.g., titanium isopropoxide, tetraethoxide, and the like. Exemplary precursor material suitable for the practice of the invention include, but are not limited to, titanium tetraisopropoxide (Ti(OC3H7)4) (hereinafter “TTIP”) and titanium tetraethoxide (Ti(OC2H5)4) (hereinafter “TTEt”). Alternatively, the titania precursor material (1) can be titanium tetrachloride.
The photoabsorption band shifting material (2) can be any material that shifts or widens the photoabsorption band of the resultant coating to extend at least partly into, or extend further into, the visible region (400 nm to 800 nm) of the electromagnetic spectrum. The material can include one or more of chromium (Cr), vanadium (V), manganese (Mn), copper (Cu), iron (Fe), magnesium (Mg), scandium (Sc), yttrium (Y), niobium (Nb), molybdenum (Mo), ruthenium (Ru), tungsten (W), silver (Ag), lead (Pb), nickel (Ni), rhenium (Re), and/or any mixtures or combinations thereof. For example, the precursor material (2) can be a metal oxide or alkoxide. In one embodiment, the material (2) is at least partially soluble, e.g., mostly soluble, in the precursor material (1). Exemplary carrier gases that can be used in the CVD method of the invention include but are not limited to air, nitrogen, oxygen, ammonia and mixtures thereof. The concentration of the precursor composition in the carrier gas can vary depending upon the specific precursor composition used. However, it is anticipated that for coatings having a thickness of about 200 Å, the concentration of precursor composition in the carrier gas will typically be in the range of 0.01 volume % to 0.1 volume %, e.g., 0.01 volume % to 0.06 volume %, e.g., 0.015 volume % to 0.06 volume %; e.g., 0.019 volume % to 0.054 volume %. For thicker coatings, the precursor compositions can be higher.
For the CVD method (as well as the spray pyrolysis method discussed below), the temperature of the substrate 22 (such as a float glass ribbon 56) during formation of the PM coating 24 thereon should be within the range which will cause the metal containing precursor composition to decompose and form a coating having a desired amount of photoactivity, e.g., photocatalytic activity, photoactive hydrophilicity, or both. The lower limit of this temperature range is largely affected by the decomposition temperature of the selected precursor composition. For the above listed titanium-containing precursors, the lower temperature limit of the substrate 22 to provide sufficient decomposition of the precursor composition is generally in the range of 400° C. (752° F.) to 500° C. (932° F.). The upper limit of this temperature range can be affected by the method of coating the substrate. For example, where the substrate 22 is a float glass ribbon 56 and the PM coating 24 is applied to the float glass ribbon 56 in the molten tin bath 50 during manufacture of the float glass ribbon 56, the float glass ribbon 56 can reach temperatures in excess of 1000° C. (1832° F.). The float glass ribbon 56 can be attenuated or sized (e.g. stretched or compressed) at temperatures above 800° C. (1472° F.). If the PM coating 24 is applied to the float glass ribbon 56 before or during attenuation, the PM coating 24 can crack or crinkle as the float glass ribbon 56 is stretched or compressed respectively. Therefore, the PM coating 24 can be applied when the float glass ribbon 56 is dimensionally stable (except for thermal contraction with cooling), e.g., below 800° C. (1472° F.) for soda lime silica glass, and the float glass ribbon 56 is at a temperature to decompose the metal-containing precursor, e.g., above 400° C. (752° F.).
For spray pyrolysis, U.S. Pat. Nos. 4,719,126; 4,719,127; 4,111,150; and 3,660,061, herein incorporated by reference, describe spray pyrolysis apparatus and methods that can be used with a conventional float glass ribbon manufacturing process. While the spray pyrolysis method like the CVD method is well suited for coating a moving float glass ribbon, the spray pyrolysis has more complex equipment than the CVD equipment and is usually employed between the exit end of the tin bath and the entrance end of the annealing lehr.
Exemplary metal-containing precursor compositions that can be used in the practice of the invention to form PM coatings by the spray pyrolysis method include relatively water insoluble organometallic reactants, specifically metal acetylacetonate compounds, which are jet milled or wet ground to a particle size of less than 10 microns and suspended in an aqueous medium by the use of a chemical wetting agent. A suitable metal acetylacetonate precursor material to form a titanium dioxide containing PM coating is titanyl acetylacetonate (TiO(C5H7O2) 2). A photoabsorption band modifying material, such as described above, can be mixed with or solubilized into the acetylacetonate precursor material. In one embodiment, the relative concentration of the metal acetylacetonate and band shifting precursor materials in the aqueous suspension ranges from 5 to 40 weight percent of the aqueous suspension. The wetting agent can be any relatively low foaming surfactant, including anionic, nonionic or cationic compositions. In one embodiment, the surfactant is nonionic. The wetting agent is typically added at 0.24% by weight, but can range from 0.01% to 1% or more. The aqueous medium can be distilled or deionized water. Aqueous suspensions for pyrolytic deposition of metal-containing films are described in U.S. Pat. No. 4,719,127 particularly at column 2, line 16, to column 4, line 48, which is herein incorporated herein by reference.
As will be appreciated by those skilled in the art, the bottom surface 60 of the float glass ribbon resting directly on the molten tin (commonly referred to as the “tin side”) has diffused tin in the surface which provides the tin side with a pattern of tin absorption that is different from the opposing surface 21 not in contact with the molten tin (commonly referred to as “the air side”). The PM coating of the invention can be formed on the air side of the float glass ribbon while it is supported on the tin by the CVD method as described above, on the air side of the float glass ribbon after it leaves the tin bath by either the CVD or spray pyrolysis methods, and/or on the tin side of the float glass ribbon after it exits the tin bath by the CVD method.
As an alternative to including oxygen in the atmosphere of the tin bath to form oxide coatings, the precursor composition can itself include one or more sources of organic oxygen. The organic oxygen can be, for example, an ester or carboxylate ester, such as an alkyl ester having an alkyl group with a β-hydrogen. Suitable esters can be alkyl esters having a C2 to C10 alkyl group. Exemplary esters which can be used in the practice of the invention are described in WO 00/75087, herein incorporated by reference.
With respect to MSVD, U.S. Pat. Nos. 4,379,040; 4,861,669; 4,900,633; 4,920,006; 4,938,857; 5,328,768; and 5,492,750, herein incorporated by reference, describe MSVD apparatus and methods to sputter coat metal oxide films on a substrate, including a glass substrate. The MSVD process is not generally compatible with providing a PM coating over a float glass ribbon during its manufacture because, among other things, the MSVD process requires reduced pressure during the sputtering operation which is difficult to form over a continuous moving float glass ribbon. However, the MSVD method is acceptable to deposit the PM coating 24 on substrate 22, e.g., a glass sheet. The substrate 22 can be heated to temperatures in the range of 400° C. (752° F.) to 500° C. (932° F.) so that the MSVD sputtered coating on the substrate crystallizes during deposition process thereby eliminating a subsequent heating operation. Heating the substrate during sputtering is not a preferred method because the additional heating operation during sputtering can decrease throughput. Alternatively, the sputter coating can be crystallized within the MSVD coating apparatus directly and without post heat treatment by using a high-energy plasma, but again because of its tendency to reduce throughput through an MSVD coater, this is not a preferred method.
An exemplary method to provide a PM coating (especially a PM coating of 300 Å or less and having an RMS surface roughness of 2 nm or less) using the MSVD method is to sputter a dopant containing coating on the substrate, remove the coated substrate from the MSVD coater, and thereafter heat treat the coated substrate to crystallize the sputter coating. For example, but not limiting to the invention, a target of titanium metal doped with at least one photoabsorption band shifting material selected from chromium (Cr), vanadium (V), manganese (Mn), copper (Cu), iron (Fe), magnesium (Mg), scandium (Sc), yttrium (Y), niobium (Nb), molybdenum (Mo), ruthenium (Ru), tungsten (W), silver (Ag), lead (Pb), nickel (Ni), rhenium (Re), and/or mixtures or combinations thereof can be sputtered in an argon/oxygen atmosphere having 5-50% oxygen, such as 20% oxygen, at a pressure of 5-10 millitorr to sputter deposit a doped titanium dioxide coating of desired thickness on the substrate 22. The coating as deposited is not crystallized. The coated substrate is removed from the coater and heated to a temperature in the range of 400° C. (752° F.) to 600° C. (1112° F.) for a time period sufficient to promote formation of the crystalline form of titanium dioxide to render photoactivity. In one embodiment, the substrate is heated for at least an hour at temperature in the range of 400° C. (752° F.) to 600° C. (1112° F.). Where the substrate 22 is a glass sheet cut from a float glass ribbon, the PM coating 24 can be sputter deposited on the air side and/or the tin side.
The substrate 22 having the PM coating 24 deposited by the CVD, spray pyrolysis or MSVD methods can be subsequently subjected to one or more post-coating annealing operations. As may be appreciated, the time and temperatures of the anneal can be affected by several factors, including the makeup of substrate 22, the makeup of PM coating 24, the thickness of the PM coating 24, and whether the PM coating 24 is directly in contact with the substrate 22 or is one layer of a multilayer stack on substrate 22.
Whether the PM coating 24 is provided by the CVD process, the spray pyrolysis process, or the MSVD process, where the substrate 22 includes sodium ions that can migrate from the substrate 22 into the PM coating 24 deposited on the substrate 22, the sodium ions can inhibit or destroy the photoactivity, e.g., photocatalytic activity and/or photoactive hydrophilicity, of the PM coating 24 by forming inactive compounds while consuming titanium, e.g., by forming sodium titanates or by causing recombination of photoexcited charges. Therefore, a sodium ion diffusion barrier (SIDB) layer can be deposited over the substrate before deposition of the PM coating 24. A suitable SIDB layer is discussed in detail in U.S. Pat. No. 6,027,766, herein incorporated by reference. With post-coating heating, a sodium barrier layer for sodium containing substrates, such as soda-lime-silica glass, can be utilized. For applying the PM coating 24 of the invention in a molten metal bath, the sodium barrier layer is optional.
The SIDB layer can be formed of amorphous or crystalline metal oxides including but not limited to cobalt oxides, chromium oxides and iron oxides, tin oxides, silicon oxides, titanium oxides, zirconium oxides, fluorine-doped tin oxides, aluminum oxides, magnesium oxides, zinc oxides, and mixtures thereof. Mixtures include but are not limited to magnesium/aluminum oxides and zinc/tin oxides. As can be appreciated by those skilled in the art, the metal oxide can include oxides, super-oxides or sub-oxides of the metal. While the thickness of the SIDB layer necessary to prevent sodium ion poisoning of the PM coating varies with several factors including the time period at which a substrate will be maintained at temperatures above which sodium ion migration occurs, the rate of sodium ion migration from the substrate, the rate of sodium ion migration through the SIDB layer, the thickness of the PM coating and the degree of photocatalytic activity required for a given application, typically for most applications, the SIDB layer thickness should be in the range of at least about 100 Å, such as at least about 250 Å, e.g., at least about 500 Å thick to prevent sodium ion poisoning of the PM coating layer. The SIDB layer can be deposited over substrate 22 by any conventional method, such as but not limited to CVD, spray pyrolysis, or MSVD methods. Where the spray pyrolysis or CVD methods are employed, the substrate 22 can be maintained at a temperature of at least about 400° C. (752° F.) to ensure decomposition of the metal-containing precursor to form the SIDB layer. The SIDB layer can be formed by other methods, including the sol-gel method, which sol-gel method as noted above is typically not compatible with the manufacture of a glass float ribbon.
A tin oxide SIDB layer, such as a fluorine doped tin oxide SIDB, can be deposited on a substrate by spray pyrolysis by forming an aqueous suspension of dibutyltin difluoride (C4H9)2SnF2 and water and applying the aqueous suspension to the substrate via spray pyrolysis. In general, the aqueous suspension typically contains between 100 to 400 grams of dibutyltin difluoride per liter of water. Wetting agents can be used as suspension enhancers. During the preparation of the aqueous suspension, the dibutyltin difluoride particles can be milled to an average particle size of 1 to 10 microns. The aqueous suspension can be vigorously agitated to provide a uniform distribution of particles in suspension. The aqueous suspension is delivered by spray pyrolysis to the surface of a substrate which is at a temperature of at least about 400° C. (752° F.), such as about 500° C. to 700° C. (932° F. to 1292° F.), whereupon the aqueous suspension pyrolyzes to form a tin oxide SIDB layer. As may be appreciated, the thickness of SIDB layer formed by this process can be controlled by, among other parameters, the coating line speed, the dibutyltin difluoride concentration in the aqueous suspension and the rate of spraying.
Alternatively the tin oxide SIDB layer can be formed by the CVD method on the substrate from a metal-containing precursor such as a monobutyltintrichloride vapor (hereinafter “MBTTCL”) in an air carrier gas mixed with water vapor. The MBTTCL vapor can be present in a concentration of at least about 0.5% in the air carrier gas applied over substrate while the substrate is at a temperature sufficient to cause the deposition of a tin containing layer e.g. at least about 400° C. (952° F.), such as about 500° C. to 800° C. (932° F. to 1472° F.), to form the tin oxide SIDB layer. As may be appreciated the thickness of the SIDB layer formed by this process can be controlled by, among other parameters, the coating line speed, the concentration of MBTTCL vapor in the air carrier gas and the rate of carrier gas flow.
An SIDB layer formed by the MSVD process is described in U.S. patent application Ser. No. 08/597,543 filed Feb. 1, 1996, entitled “Alkali Metal Diffusion Barrier Layer”, herein incorporated by reference, which discloses the formation of alkali metal diffusion barriers. The barrier layer disclosed therein is generally effective at thicknesses of about 20 Å to about 180 Å, with effectiveness increasing as the density of the barrier increases.
The PM coatings 24 of the present invention can be photoactive, e.g., photocatalytic and/or photoactively hydrophilic, upon exposure to radiation in the ultraviolet range, e.g., 300 nm to 400 nm, and/or visible range (400 nm to 800 nm) of the electromagnetic spectrum. Sources of ultraviolet radiation include natural sources, e.g., solar radiation, and artificial sources such as a black light or an ultraviolet light source such as a UVA-340 light source commercially available from the Q-Panel Company of Cleveland, Ohio.
As shown in
The functional coating 46 can be an electrically conductive coating, such as, for example, an electrically conductive heated window coating as disclosed in U.S. Pat. Nos. 5,653,903 and 5,028,759, or a single-film or multi-film coating capable of functioning as an antenna. Likewise, the functional coating 46 can be a solar control coating, for example, a visible, infrared or ultraviolet energy reflecting or absorbing coating. Examples of suitable solar control coatings are found, for example, in U.S. Pat. Nos. 4,898,789; 5,821,001; 4,716,086; 4,610,771; 4,902,580; 4,716,086; 4,806,220; 4,898,790; 4,834,857; 4,948,677; 5,059,295; and 5,028,759, and also in U.S. patent application Ser. No. 09/058,440. Similarly, the functional coating 46 can be a low emissivity coating. “Low emissivity coatings” allow visible wavelength energy, e.g., 400 nm to about 800 nm (e.g., to about 780 nm), to be transmitted through the coating but reflect longer-wavelength solar infrared energy and/or thermal infrared energy and are typically intended to improve the thermal insulating properties of architectural glazings. By “low emissivity” is meant emissivity less than 0.4, such as less than 0.3, e.g., less than 0.2. Examples of low emissivity coatings are found, for example, in U.S. Pat. Nos. 4,952,423 and 4,504,109 and British reference GB 2,302,102. The functional coating 46 can be a single layer or multiple layer coating and can comprise one or more metals, non-metals, semi-metals, semiconductors, and/or alloys, compounds, composites, combinations, or blends thereof. For example, the functional coating 46 can be a single layer metal oxide coating, a multiple layer metal oxide coating, a non-metal oxide coating, or a multiple layer coating.
Examples of suitable functional coatings for use with the invention are commercially available from PPG Industries, Inc. of Pittsburgh, Pa. under the SUNGATE® and SOLARBAN® families of coatings. Such functional coatings typically include one or more anti-reflective coating films comprising dielectric or anti-reflective materials, such as metal oxides or oxides of metal alloys, which are preferably transparent or substantially transparent to visible light. The functional coating 46 can also include infrared reflective films comprising a reflective metal, e.g., a noble metal such as gold, copper or silver, or combinations or alloys thereof, and can further comprise a primer film or barrier film, such as titanium, as is known in the art, located over and/or under the metal reflective layer.
The functional coating 46 can be deposited in any conventional manner, such as but not limited to magnetron sputter vapor deposition (MSVD), chemical vapor deposition (CVD), spray pyrolysis (i.e., pyrolytic deposition), atmospheric pressure CVD (APCVD), low-pressure CVD (LPCVD), plasma-enhanced CVD (PEVCD), plasma assisted CVD (PACVD), thermal or electron-beam evaporation, cathodic arc deposition, plasma spray deposition, and wet chemical deposition (e.g., sol-gel, mirror silvering etc.). For example, U.S. Pat. Nos. 4,584,206, 4,900,110, and 5,714,199, herein incorporated by reference, disclose methods and apparatus for depositing a metal containing film on the bottom surface of a glass ribbon by chemical vapor deposition. Such a known apparatus can be located downstream of the molten tin bath in the float glass process to provide a functional coating on the underside of the glass ribbon, i.e., the side opposite the PM coating of the invention. Alternatively, one or more other CVD coaters can be located in the tin bath to deposit a functional coating either above or below the PM coating 24 on the float glass ribbon. When the functional coating is applied on the PM coating side of the substrate, the functional coating can be applied in the tin bath before the PM coating. When the functional coating is on the opposite side 60 from the PM coating, the functional coating can be applied after the tin bath in the float process as discussed above, e.g., on the tin side of the substrate 22 by CVD or MSVD. In another embodiment, the PM coating 24 can be deposited over all or a portion of the surface 60 and the functional coating 46 can be deposited over all or a portion of the surface 21.
An exemplary article of manufacture of the invention is shown in
Advantages of the present invention over the ion-implantation and sol-gel methods of forming self-cleaning coatings include an ability to form a thin, dense, PM film on a substrate as opposed to the generally thicker, porous self-cleaning coatings obtained with the ion-implantation and sol-gel coating methods. Still another advantage is that the method of providing a PM coating according to the present invention avoids the need to reheat the substrate after application of the coating or coating precursor as is practiced in the conventional ion-implantation and sol-gel methods. Not only does this render the present method less costly and more efficient, e.g., less equipment costs, less energy costs, and less production time, but also the opportunity for sodium ion migration and in turn sodium ion poisoning of the PM coating 24 of the present invention is significantly reduced. Further still, the method of the present invention is easily adapted to the formation of PM coatings on continuous moving substrates, such as a glass float ribbon.
It will be readily appreciated by those skilled in the art that modifications can be made to the invention without departing from the concepts disclosed in the foregoing description. Accordingly, the particular embodiments described in detail herein are illustrative only and are not limiting to the scope of the invention, which is to be given the full breadth of the appended claims and any and all equivalents thereof.
|Cited Patent||Filing date||Publication date||Applicant||Title|
|US3630796||Jun 10, 1968||Dec 28, 1971||Matsushita Electronics Corp||Process for forming a titanium dioxide film|
|US3660061||Mar 5, 1970||May 2, 1972||Ppg Industries Inc||Coated glass sheet and method for making the same|
|US4017661||Jan 19, 1976||Apr 12, 1977||Ppg Industries, Inc.||Electrically conductive transparent laminated window|
|US4111150||Mar 28, 1977||Sep 5, 1978||Ppg Industries, Inc.||Apparatus for coating an advancing substrate|
|US4112142||Aug 21, 1972||Sep 5, 1978||Glaswerk Schott & Gen.||Method for the production of light-reflecting layers on a surface of a transparent glass article|
|US4123244||Mar 28, 1977||Oct 31, 1978||Bfg Glassgroup||Process of forming a metal or metal compound coating on a face of a glass substrate and apparatus suitable for use in forming such coating|
|US4193236||Jan 30, 1978||Mar 18, 1980||Ppg Industries, Inc.||Multiple glazed unit having an adhesive cleat|
|US4238276||Mar 16, 1979||Dec 9, 1980||Hitachi, Ltd.||Process for producing liquid crystal display element|
|US4329379||Oct 17, 1979||May 11, 1982||Bfg Glassgroup||Process for forming tin oxide glass coating|
|US4344986||Aug 8, 1980||Aug 17, 1982||Ppg Industries, Inc.||Method of delivering powder coating reactants|
|US4351267||Feb 18, 1981||Sep 28, 1982||Societe Italiana Vetro-Siv-S.P.A.||Apparatus for continuously depositing a layer of a solid material on the surface of a substrate heated to a high temperature|
|US4379040||Feb 18, 1982||Apr 5, 1983||Ppg Industries, Inc.||Method of and apparatus for control of reactive sputtering deposition|
|US4393095||Feb 1, 1982||Jul 12, 1983||Ppg Industries, Inc.||Chemical vapor deposition of vanadium oxide coatings|
|US4400412||Feb 1, 1982||Aug 23, 1983||Ppg Industries, Inc.||Thermochromic vanadium oxide coated glass|
|US4464874||Nov 3, 1982||Aug 14, 1984||Hordis Brothers, Inc.||Window unit|
|US4466562||Dec 15, 1981||Aug 21, 1984||Ppg Industries, Inc.||Method of and apparatus for severing a glass sheet|
|US4485146||Jul 29, 1982||Nov 27, 1984||Asahi Glass Company Ltd||Glass body provided with an alkali diffusion-preventing silicon oxide layer|
|US4504109||Nov 19, 1982||Mar 12, 1985||Kabushiki Kaisha Toyota Chuo Kenkyusho||Infrared shielding lamination|
|US4544470||May 31, 1984||Oct 1, 1985||Ford Motor Company||Electrochemical photocatalytic structure|
|US4584206||Jul 30, 1984||Apr 22, 1986||Ppg Industries, Inc.||Chemical vapor deposition of a reflective film on the bottom surface of a float glass ribbon|
|US4610771||Oct 29, 1984||Sep 9, 1986||Ppg Industries, Inc.||Sputtered films of metal alloy oxides and method of preparation thereof|
|US4671155||Jun 13, 1985||Jun 9, 1987||Ppg Industries, Inc.||Positioning apparatus|
|US4716086||Dec 23, 1985||Dec 29, 1987||Ppg Industries, Inc.||Protective overcoat for low emissivity coated article|
|US4719126||Feb 2, 1983||Jan 12, 1988||Ppg Industries, Inc.||Pyrolytic deposition of metal oxide film from aqueous suspension|
|US4719127||Feb 2, 1983||Jan 12, 1988||Ppg Industries, Inc.||Aqueous chemical suspension for pyrolytic deposition of metal-containing film|
|US4746347||Jan 2, 1987||May 24, 1988||Ppg Industries, Inc.||Patterned float glass method|
|US4751149||Mar 12, 1987||Jun 14, 1988||Atlantic Richfield Company||Chemical vapor deposition of zinc oxide films and products|
|US4792536||Jun 29, 1987||Dec 20, 1988||Ppg Industries, Inc.||Transparent infrared absorbing glass and method of making|
|US4806220||Dec 29, 1986||Feb 21, 1989||Ppg Industries, Inc.||Method of making low emissivity film for high temperature processing|
|US4834857||Apr 1, 1988||May 30, 1989||Ppg Industries, Inc.||Neutral sputtered films of metal alloy oxides|
|US4853257||Sep 30, 1987||Aug 1, 1989||Ppg Industries, Inc.||Chemical vapor deposition of tin oxide on float glass in the tin bath|
|US4861669||Mar 26, 1987||Aug 29, 1989||Ppg Industries, Inc.||Sputtered titanium oxynitride films|
|US4878934||Jan 19, 1988||Nov 7, 1989||Glaverbel||Process and apparatus for coating glass|
|US4888038||Feb 12, 1988||Dec 19, 1989||Libbey-Owens-Ford Co.||Apparatus and method for tempering glass sheets|
|US4892712||Sep 4, 1987||Jan 9, 1990||Nutech Energy Systems Inc.||Fluid purification|
|US4898789||Apr 4, 1988||Feb 6, 1990||Ppg Industries, Inc.||Low emissivity film for automotive heat load reduction|
|US4898790||Apr 1, 1988||Feb 6, 1990||Ppg Industries, Inc.||Low emissivity film for high temperature processing|
|US4900110||Dec 16, 1985||Feb 13, 1990||Ppg Industries, Inc.||Chemical vapor deposition of a reflective film on the bottom surface of a float glass ribbon|
|US4900633||Mar 26, 1987||Feb 13, 1990||Ppg Industries, Inc.||High performance multilayer coatings|
|US4902580||Oct 21, 1988||Feb 20, 1990||Ppg Industries, Inc.||Neutral reflecting coated articles with sputtered multilayer films of metal oxides|
|US4920006||Mar 26, 1987||Apr 24, 1990||Ppg Industries, Inc.||Colored metal alloy/oxynitride coatings|
|US4938857||Nov 27, 1989||Jul 3, 1990||Ppg Industries, Inc.||Method for making colored metal alloy/oxynitride coatings|
|US4948677||Mar 17, 1986||Aug 14, 1990||Ppg Industries, Inc.||High transmittance, low emissivity article and method of preparation|
|US4952423||Jan 27, 1988||Aug 28, 1990||Saint-Gobain Recherche||Production of a transparent electric conductor|
|US4971843||Aug 23, 1985||Nov 20, 1990||Ppg Industries, Inc.||Non-iridescent infrared-reflecting coated glass|
|US4995893||Jun 22, 1989||Feb 26, 1991||Pilkington Plc||Method of making coatings on glass surfaces|
|US4997576||Sep 25, 1989||Mar 5, 1991||Board Of Regents, The University Of Texas System||Materials and methods for photocatalyzing oxidation of organic compounds on water|
|US5028568||Jul 5, 1989||Jul 2, 1991||Wisconsin Alumni Research Foundation||Niobium-doped titanium membranes|
|US5028759||Apr 3, 1989||Jul 2, 1991||Ppg Industries, Inc.||Low emissivity film for a heated windshield|
|US5032241||Sep 7, 1989||Jul 16, 1991||Nutech Energy Systems Inc.||Fluid purification|
|US5035784||Jun 18, 1990||Jul 30, 1991||Wisconsin Alumni Research Foundation||Degradation of organic chemicals with titanium ceramic membranes|
|US5041150||Oct 12, 1989||Aug 20, 1991||Pilkington Plc||Process for coating glass|
|US5059295||Feb 15, 1990||Oct 22, 1991||Ppg Industries, Inc.||Method of making low emissivity window|
|US5088258||Sep 7, 1990||Feb 18, 1992||Weather Shield Mfg., Inc.||Thermal broken glass spacer|
|US5106663||Mar 7, 1989||Apr 21, 1992||Tremco Incorporated||Double-paned window system having controlled sealant thickness|
|US5165972||Mar 27, 1992||Nov 24, 1992||Pilkington Plc||Coated glass|
|US5194161||Mar 5, 1992||Mar 16, 1993||Board Of Regents, The University Of Texas System||Materials and methods for enhanced photocatalyzation of organic compounds with palladium|
|US5240886||Jul 30, 1990||Aug 31, 1993||Ppg Industries, Inc.||Ultraviolet absorbing, green tinted glass|
|US5244692||Dec 6, 1991||Sep 14, 1993||Saint-Gobain Vitrage International||Process for formation of an aluminum oxide-based layer on glass, the product thus obtained, and its use in windows incorporating a conductive layer|
|US5256616||Dec 14, 1990||Oct 26, 1993||Board Of Regents, The University Of Texas System||Materials and methods for photocatalyzing oxidation of organic compounds on water|
|US5304394||Jun 12, 1992||Apr 19, 1994||Saint-Gobain Vitrage International||Technique for forming, by pyrolysis in a gaseous process, a coating based essentially upon oxygen and silicon|
|US5308458||Jan 27, 1992||May 3, 1994||Tioxide Group Services Limited||Destruction process|
|US5308805||May 5, 1993||May 3, 1994||Libbey-Owens-Ford Co.||Neutral, low transmittance glass|
|US5328768||Nov 29, 1991||Jul 12, 1994||Ppg Industries, Inc.||Durable water repellant glass surface|
|US5342676||Nov 24, 1992||Aug 30, 1994||Saint-Gobain Vitrage International||Glass substrate provided with a low emissivity film|
|US5348805||Feb 5, 1993||Sep 20, 1994||Saint-Gobain Vitrage International||Formation of a layer of aluminum and tin or titanium oxides on a glass substrate|
|US5368892||Apr 12, 1993||Nov 29, 1994||Saint-Gobain Vitrage International||Non-wettable glass sheet|
|US5385872||Mar 26, 1992||Jan 31, 1995||Ppg Industries, Inc.||Ultraviolet absorbing green tinted glass|
|US5389427||Jan 24, 1994||Feb 14, 1995||Saint-Gobain Vitrage International||Non-wettable glass sheet|
|US5393593||Oct 12, 1993||Feb 28, 1995||Ppg Industries, Inc.||Dark gray, infrared absorbing glass composition and coated glass for privacy glazing|
|US5464657||Jun 23, 1994||Nov 7, 1995||Ppg Industries, Inc.||Method for coating a moving glass substrate|
|US5478783||Aug 3, 1994||Dec 26, 1995||Libbey-Owens-Ford Co.||Glass compositions|
|US5492750||Sep 26, 1994||Feb 20, 1996||Ppg Industries, Inc.||Mask for coated glass|
|US5505989||Jul 8, 1993||Apr 9, 1996||Pilkington Glass Limited||Method for coating a hot glass ribbon|
|US5514454||Nov 1, 1994||May 7, 1996||Saint-Gobain Vitrage||Transparent substrate provided with a metal nitride layer|
|US5522911||Jan 6, 1994||Jun 4, 1996||Glaverbel||Device and method for forming a coating by pyrolysis|
|US5525406||Jun 7, 1995||Jun 11, 1996||Libbey-Owens-Ford Co.||Coatings on glass|
|US5536718||Jan 17, 1995||Jul 16, 1996||American Cyanamid Company||Tricyclic benzazepine vasopressin antagonists|
|US5547823||Nov 9, 1995||Aug 20, 1996||Ishihara Sangyo Kaisha, Ltd.||Photocatalyst composite and process for producing the same|
|US5580364||Jan 10, 1994||Dec 3, 1996||Libbey-Owens-Ford Co.||Method of producing a coated glass substrate exhibiting reflected color|
|US5595813||Sep 15, 1993||Jan 21, 1997||Takenaka Corporation||Architectural material using metal oxide exhibiting photocatalytic activity|
|US5599387||Jun 7, 1995||Feb 4, 1997||Ppg Industries, Inc.||Compounds and compositions for coating glass with silicon oxide|
|US5616532||Oct 21, 1994||Apr 1, 1997||E. Heller & Company||Photocatalyst-binder compositions|
|US5618579||Aug 12, 1994||Apr 8, 1997||Saint-Gobain Vitrage||Process for the vapor deposition of a metal nitride-based layer on a transparent substrate|
|US5643436||Jun 7, 1995||Jul 1, 1997||Takenaka Corporation||Architectural material using metal oxide exhibiting photocatalytic activity|
|US5653903||Jun 27, 1995||Aug 5, 1997||Ppg Industries, Inc.||L-shaped heating element with radiused end for a windshield|
|US5698262||May 6, 1996||Dec 16, 1997||Libbey-Owens-Ford Co.||Method for forming tin oxide coating on glass|
|US5714199||Jun 7, 1995||Feb 3, 1998||Libbey-Owens-Ford Co.||Method for applying a polymer powder onto a pre-heated glass substrate and the resulting article|
|US5735922||Feb 28, 1997||Apr 7, 1998||Pilkington Glass Limited||Method of bending and tempering glass sheets|
|US5736055||May 16, 1995||Apr 7, 1998||Photo-Catalytics, Inc.||Cartridge for photocatalytic purification of fluids|
|US5745291||Feb 10, 1997||Apr 28, 1998||Pilkington Glass Limited||Mirror including a glass substrate and a pyrolytic silicon reflecting layer|
|US5749931||Jun 7, 1995||May 12, 1998||Libbey-Owens-Ford Co.||Coatings on glass|
|US5751484||Dec 3, 1996||May 12, 1998||Libbey-Owens-Ford Co.||Coatings on glass|
|US5753322||Apr 19, 1996||May 19, 1998||Ykk Corporation||Antibacterial, antifungal aluminum building materials and fixtures using the materials|
|US5755845||Jan 3, 1997||May 26, 1998||Pilkington Glass Limited||Method and apparatus for bending and tempering glass sheets|
|US5755867||Dec 20, 1996||May 26, 1998||Shin-Etsu Chemical Co., Ltd.||Photocatalytic hydrophilic coating compositions|
|US5764415||Jan 9, 1995||Jun 9, 1998||Pilkington Glass Limited||Coatings on glass|
|US5773086||Aug 13, 1996||Jun 30, 1998||Libbey-Owens-Ford Co.||Method of coating flat glass with indium oxide|
|US5821001||Feb 27, 1997||Oct 13, 1998||Ppg Industries, Inc.||Coated articles|
|US5830252||Feb 1, 1996||Nov 3, 1998||Ppg Industries, Inc.||Alkali metal diffusion barrier layer|
|US5853866||Dec 9, 1994||Dec 29, 1998||Toto Ltd.||Multi-functional material with photocalytic functions and method of manufacturing same|
|US5854169||May 9, 1997||Dec 29, 1998||E. Heller & Company||Photocatalyst-binder compositions|
|US5854708||Jul 21, 1997||Dec 29, 1998||Murakami Corporation||Anti-fog element|
|US5869187||Feb 28, 1997||Feb 9, 1999||Nissan Motor Co., Ltd.||Defogging article and method of producing same|
|US5873203||Sep 2, 1997||Feb 23, 1999||Ppg Industries, Inc.||Photoelectrolytically-desiccating multiple-glazed window units|
|US5939194||Dec 9, 1997||Aug 17, 1999||Toto Ltd.||Photocatalytically hydrophilifying and hydrophobifying material|
|US5939201||Mar 6, 1997||Aug 17, 1999||Saint-Gobain Vitrage||Method for depositing a reflective layer on glass, and products obtained|
|US5961843||Oct 5, 1995||Oct 5, 1999||Toto Ltd.||Antimicrobial solid material, process for producing the same, and method of utilizing the same|
|US5980983||Apr 17, 1998||Nov 9, 1999||The President And Fellows Of Harvard University||Liquid precursors for formation of metal oxides|
|US6001462||Mar 6, 1996||Dec 14, 1999||Libbey-Owens-Ford Co.||Laminated glazing unit with polyvinyl chloride interlayer|
|US6013372||Sep 19, 1997||Jan 11, 2000||Toto, Ltd.||Method for photocatalytically rendering a surface of a substrate superhydrophilic, a substrate with superhydrophilic photocatalytic surface, and method of making thereof|
|US6027766||Jul 23, 1997||Feb 22, 2000||Ppg Industries Ohio, Inc.||Photocatalytically-activated self-cleaning article and method of making same|
|US6027797||Oct 7, 1998||Feb 22, 2000||Toto Ltd.||Multi-functional material with photocatalytic functions and method of manufacturing same|
|US6037289||Sep 13, 1996||Mar 14, 2000||Rhodia Chimie||Titanium dioxide-based photocatalytic coating substrate, and titanium dioxide-based organic dispersions|
|US6045896||Dec 12, 1997||Apr 4, 2000||Saint-Gobain Vitrage||Glazing assembly comprising a substrate provided with a stack of thin layers for solar protection and/or thermal insulation|
|US6054227||Jul 23, 1997||Apr 25, 2000||Ppg Industries Ohio, Inc.||Photocatalytically-activated self-cleaning appliances|
|US6068914||May 14, 1997||May 30, 2000||Saint-Gobain Vitrage||Glazing pane having an anti-reflection coating|
|US6074981||Aug 1, 1997||Jun 13, 2000||Nippon Sheet Glass Co., Ltd.||Photocatalyst and process for the preparation thereof|
|US6077492||Jan 22, 1997||Jun 20, 2000||Petroleum Energy Center||Photocatalyst, process for producing the photocatalyst, and photocatalytic reaction method|
|US6090489||Jun 19, 1998||Jul 18, 2000||Toto, Ltd.||Method for photocatalytically hydrophilifying surface and composite material with photocatalytically hydrophilifiable surface|
|US6103360||Jan 9, 1998||Aug 15, 2000||Armstrong World Industries, Inc.||High light reflectance and durable ceiling board coating|
|US6103363||Sep 13, 1996||Aug 15, 2000||Saint-Gobain Recherche||Substrate with a photocatalytic coating|
|US6106955||Jan 12, 1998||Aug 22, 2000||Takenaka Corporation||Metal material having photocatalytic activity and method of manufacturing the same|
|US6132881 *||Sep 16, 1997||Oct 17, 2000||Guardian Industries Corp.||High light transmission, low-E sputter coated layer systems and insulated glass units made therefrom|
|US6165256||Jan 15, 1999||Dec 26, 2000||Toto Ltd.||Photocatalytically hydrophilifiable coating composition|
|US6191062||Nov 16, 1995||Feb 20, 2001||Toto Ltd.||Photocatalytic functional material and method for producing the same|
|US6210779||Oct 7, 1998||Apr 3, 2001||Toto Ltd.||Multi-functional material with photocatalytic functions and method of manufacturing same|
|US6228480||Jun 18, 1996||May 8, 2001||Nippon Soda Co., Ltd.||Photocatalyst-carrying structure and photocatalyst coating material|
|US6238738||Sep 7, 2000||May 29, 2001||Libbey-Owens-Ford Co.||Method for depositing titanium oxide coatings on flat glass|
|US6294246||Oct 7, 1998||Sep 25, 2001||Toto Ltd.||Multi-functional material with photocatalytic functions and method of manufacturing same|
|US6294247||Oct 7, 1998||Sep 25, 2001||Toto Ltd.||Multi-functional material with photocatalytic functions and method of manufacturing same|
|US6322881||Feb 29, 2000||Nov 27, 2001||Saint-Gobain Vitrage||Glazing assembly comprising a substrate provided with a stack of thin layers for solar protection and/or thermal insulation|
|US6326079||Jul 13, 2000||Dec 4, 2001||Saint-Gobain Glass France||Substrate with a photocatalytic coating|
|US6387844||Mar 17, 1998||May 14, 2002||Akira Fujishima||Titanium dioxide photocatalyst|
|US6413581||Apr 1, 1999||Jul 2, 2002||Ppg Industries Ohio, Inc.||Photocatalytically-activated self-cleaning article and method of making same|
|US6495251||Apr 9, 1998||Dec 17, 2002||Ppg Industries Ohio, Inc.||Silicon oxynitride protective coatings|
|US6537379 *||Jan 13, 2000||Mar 25, 2003||Hrl Laboratories, Llc||Photocatalytic coating and method for cleaning spacecraft surfaces|
|US6576344 *||May 24, 2000||Jun 10, 2003||Nippon Sheet Glass Co., Ltd.||Photocatalyst article, anti-fogging, anti-soiling articles, and production method of anti-fogging, anti-soiling articles|
|US6722159||Feb 14, 2002||Apr 20, 2004||Ppg Industries Ohio, Inc.||Photocatalytically-activated self-cleaning article and method of making same|
|US6761984 *||Dec 21, 2000||Jul 13, 2004||Nippon Sheet Glass Co., Ltd.||Article coated with photocatalyst film, method for preparing the article and sputtering target for use in coating with the film|
|US7096692||Jul 11, 2002||Aug 29, 2006||Ppg Industries Ohio, Inc.||Visible-light-responsive photoactive coating, coated article, and method of making same|
|US20010022497 *||Feb 22, 2001||Sep 20, 2001||Dai Nippon Printing Co.,||Electroluminescent device and process for producing the same|
|US20020031674 *||Feb 27, 2001||Mar 14, 2002||Laird Ronald E.||Low-emissivity glass coatings having a layer of silicon oxynitride and methods of making same|
|US20020150531 *||May 26, 2000||Oct 17, 2002||Masahiro Ohmori||Perovskite titanium-type composite oxide particle and productionprocess thereof|
|EP0071865B1||Jul 26, 1982||Oct 23, 1985||Asahi Glass Company Ltd.||Glass body provided with an alkali diffusion-preventing silicon oxide layer|
|EP0348185B1||Jun 22, 1989||Aug 26, 1992||Pilkington Plc||Coatings on glass|
|EP0489621B1||Nov 26, 1991||Aug 2, 1995||Saint-Gobain Vitrage||Process of making an alumina layer on glass, product obtained and its use in glazings with conducting layer|
|EP0544577B1||Nov 24, 1992||May 28, 1997||Saint-Gobain Vitrage||Glass substrate coated with a low emissivity coating|
|EP0581216B1||Jul 23, 1993||Jan 8, 1997||Ishihara Sangyo Kaisha, Ltd.||Process for producing coating films of titanium oxide|
|EP0590477B2||Sep 21, 1993||Oct 13, 2004||Takenaka Corporation||Architectural material using metal oxide exhibiting photocatalytic activity|
|EP0633064B1||Jun 23, 1994||Dec 23, 1998||Akira Fujishima||Photocatalyst composite and process for producing the same|
|EP0636702B1||Jul 26, 1994||May 19, 1999||Asahi Glass Company Ltd.||Methods for producing functional films|
|EP0650938B1||Oct 27, 1994||Dec 29, 1999||Saint-Gobain Vitrage||Transparent substrate coated with a metallic nitride layer|
|EP0675086A2||Jul 23, 1993||Oct 4, 1995||Ishihara Sangyo Kaisha, Ltd.||Process for producing particles of titanium oxide, their use as photocatalyst and a process for removing noxious materials|
|EP0684075B1||Dec 9, 1994||Mar 26, 2003||Toto Ltd.||Multi-functional material having photo-catalytic function and production method therefor|
|EP0737513B1||Oct 30, 1995||May 29, 2002||Kanagawa Academy Of Science And Technology||Titanium oxide photocatalyst structure and method of manufacturing the same|
|EP0770579A1||Oct 28, 1996||May 2, 1997||Asahi Glass Company Ltd.||Modified titanium oxide sol, photocatalyst composition and photocatalyst composition-forming agent|
|EP0780158B1||Dec 19, 1996||Jun 13, 2001||Asahi Glass Company Ltd.||Photocatalyst composition and process for its production, and photocatalyst composition attached substrate|
|EP0784034B1||Sep 14, 1996||Aug 8, 2001||Matsushita Electric Works, Ltd.||Titanium dioxide film having photocatalytic activity and substrate having the same|
|EP0816466B1||Mar 21, 1996||May 17, 2006||Toto Ltd.||Use of material having ultrahydrophilic and photocatalytic surface|
|EP0818239B1||Jan 22, 1997||Aug 6, 2003||Petroleum Energy Center||Photocatalyst, method of producing the photocatalyst, and photocatalytic reaction method|
|EP0820967B1||Jul 23, 1997||Sep 29, 2004||Murakami Corporation||Anti-fog element|
|EP1066878B1||Sep 28, 1999||Mar 15, 2006||Nippon Sheet Glass Co., Ltd.||Photocatalyst article, article prevented from fogging and fouling, and process for producing article prevented from fogging and fouling|
|GB1523991A||Title not available|
|GB1524326A||Title not available|
|GB2026454A||Title not available|
|GB2031756B||Title not available|
|GB2150044B||Title not available|
|GB2302102B||Title not available|
|GB2320499A||Title not available|
|GB2320503A||Title not available|
|GB2324098A||Title not available|
|GB2355273A||Title not available|
|GB2361246A||Title not available|
|WO2001046488A1 *||Dec 21, 2000||Jun 28, 2001||Nippon Sheet Glass Co., Ltd.||Article coated with photocatalyst film, method for preparing the article and sputtering target for use in coating with the film|
|1||"Solar Control Glazing News From Glaverbel", Glass, Nov. 1993.|
|2||"SSG Antelio Solar Control Glass", Saint-Gobain Glass Comfort, undated.|
|3||"Transparent, Photocatalytic TiO2 Film Formed on Glass", Japan Chemical Week, Dec. 15, 1994, pp. 1, 2, 4, 8.|
|4||A. Heller, "Chemistry and Applications of Photocatalytic Oxidation of Thin Organic Films", Acc. Chem. Res. (1995), pp. 503-508.|
|5||Anpo, M. et al, The Utilization of Visible Light by Titanium Dioxide Potocatalysts Modified by a Metal Ion Implantation Method, Electrochemical Society Proceedings, vol. 97-20, (199) pp. 331-334.|
|6||Anpo, M. et al., Design of unique titanium oxide photocatalysts by an advanced metal ion-implantation method and photocatalytic reactions under visible light irradiation, "Res. Chem. Intermed.", vol. 24, No. 2, pp. 143-149 (1998).|
|7||Anpo, M. et al., The design and development of second-generation titanium oxide photocatalysts able to operate under visible light irradiation by applying a metal ion-implantation method, "Res. Chem. Intermed.", vol. 27, No. 4,5, pp. 459-467 (2001).|
|8||Anpo, M., Applications of titanium oxide photocatalysts and unique second-generation TiO2 photocatalysts able to operate under visible light irradiation for the reduction of environmental toxins on a global scale, "Studies in Surface Science and Catalysis", 130, pp. 157-166.|
|9||Anpo, M., Photocatalysis on titanium oxide catalysts "Catalysis Surveys from Japan", (1997), pp. 169-179.|
|10||Anpo, Masakazu et al., Design and development of second-generation titanium oxide photocatalysts to better our environment-approaches in realizing the use of visible light, "International Journal of Photoenergy", vol. 3, (2001) pp. 89-94.|
|11||Anpo, Masakazu et al., Design and development of unique titanium oxide photocatalysts capable of operating under visible light irradiation by an advanced metal ion-implantation method, "Science and Technology in Catalysis", 1998, pp. 305-310.|
|12||Anpo, Masakazu et al., The utilization of visible light by titanium dioxide photocatalysts modified by a metal ion implantation method, "Electrochemical Society Proceedings", vol. 97-20, pp. 331-334.|
|13||Anpo, Masakazu, et al., Design and development of a titanium oxide photocatalyst able to work effectively under visible light irradiation by an advanced metal ion-implantation method, "Hyomen Kagaku" (1999) vol. 20, No. 2, pp. 60-65.|
|14||Anpo, Masakazu, Use of Visible Light. Second-Generation Titanium Oxide Photocatalysts Prepared by the Application of an Advanced Metal Ion-Implantation Method, Pure Appl. Chem., vol. 72, No. 9, pp. 1787-1792 (2000).|
|15||Application of ion implantation method and magnetron sputter vapor deposit, Jun. 2000, vol. 48, No. 6, pp. 31-36.|
|16||Apr. 3, 2000 Letter From Mrs. Colette Ward, Patent Litigation Enquiries, British Library.|
|17||Asahi, R. et al., Visible-light photocatalysis in nitrogen-doped titanium oxides, "Science", vol. 293 (2001) pp. 269-271.|
|18||B. Samuneva et al., "Sol-gel processing of titanium-containing thin coatings, Part I Preparation and structure", Journal of Materials Science 28 (1993), pp. 2353-2360.|
|19||Bach et al.; Kristallstruktur and Optische Eigenshaften von Dunnen Organogenen Titanoxyd-Schichten Auf Glasunterlagen [Crystal Structure and Optical Properties of Thin Organogenic Titanium Oxide Layers on Glass Substrates], Thin Solid Films 1 (1967/68), pp. 255-276.|
|20||C. Greenberg, Thin Films on Float Glass: The Extraordinary Possibilities, Industrial Engineering Chemistry & Research, vol. 40, No. 1, pp. 26-32, 2001.|
|21||C. Trapalis et al., "Sol-gel processing of titanium-containing thin coatings, Part II XPS Studies", Journal of Materials Science 28 (1993), pp. 1276-1282.|
|22||Chemical Abstracts, 116 89812a, Sokolov, et al. "Selective Activation of Smooth Surfaces of Glass and Ceramic Articles Before Chemical Metalization," Abstract only.|
|23||D. R. Uhlmann, "Glass: Science and Technology", vol. 2, Processing I, pp. 253-284 (1984).|
|24||Fukayama, S. et al., "Highly Transparent and Photoactive TiO2 Thin Film Coated on Glass Substrate", 187th Electrochemical Society Meeting, Abstract No. 735, Extended Abstracts 95-1, (available at least by Mar. 1995), pp. 1102-1103.|
|25||G. Colon et al., "Photocatalytic deactivation of commercial TiO2 sample during simultaneous photoreduction of Cr(VI) and photooxidation of salicylic acid", Journal of Photochemistry and Photobiology A: Chemistry 138 (2001), pp. 79-85.|
|26||GlassFAQs, Glass FACTS.com, p. 1-5.|
|27||Guang-Hai, Li et al., Effect of ZnFe2O4 doping on the optical properties of TiO2 thin films, "Chinese Physics", vol. 10, No. 2, Feb. 2001, pp. 148-151.|
|28||H. H. Dunken, Glass Surfaces, Treatise on Materials Science and Technology, Vo. 22, pp. 1-75, 1982.|
|29||H. Tada, "Photoinduced Oxidation of Methylsiloxane Monolayers Chemisorbed on TiO2", Langmuir 1996, 12, pp. 966-971.|
|30||Hass, Georg, "Oxide Layers Deposited from Organic Solutions", Physics of Thin Films, 1969, pp. 87 and 105-115, vol. 5, Academic Press, New York and London.|
|31||Hass, George et al., Physics of Thin Films, vol. 5, Academic Press, New York, 1969, p. 237, pp. 304-406.|
|32||I. Sopyan et al., "Highly Efficient TiO2 Film Photocatalyst, Degradation of Gaseous Acetaldehyde", Chemistry Letters (1994) pp. 723-726.|
|33||Ihara, T., et al., Preparation of a visible-light-active TiO2 photocatalyst by RF plasma treatment, "Journal of Materials Science", 36 (2001) pp. 4201-4207.|
|34||Imura, S. et al., Improvement of the photocatalytic activity of titanium oxide by x-ray irradiation, "Electrochemistry", vol. 5, 324-328 (2001).|
|35||Iwasaki, M. et al., Cobalt ion-doped TiO2 photocatalyst response to visible light, "Journal of Colloid and Interface Science" 224, (2000), pp. 202-204.|
|36||J. Papp et al., "Titanium(IV) Oxide Photocatalysts with Palladium", Chem. Mater. 1993, 5, pp. 284-288.|
|37||JP 88-158890, Abstract Only, Derwent JP 860243762, Glass Article Difficult Soil Coating Thin Titanium DI Oxide Coating Contain Platinum@Rhodium Palladium@.|
|38||K. G. Geraghty et al., "Kinetics of the Reactive Sputter Deposition of Titanium Oxides", Journal of the Electrochemical Society (1976), pp. 1201-1207.|
|39||K. Hashimoto et al., TiO2 Coated Glass with Self-Cleaning Function, Kagaku To Kogyou (Chemistry and Industry), vol. 48, No. 10, p. 1256-1258 (1995).|
|40||Kamata, Kiichiro et al., "Rapid Formation of TiO2 Films by a Conventional CVD Method", Journal of Materials Science, Letters 9, 1990, pp. 316-319, Chapman and Hall Ltd.|
|41||Kiernan, Vincent, "A Clearer View for Car Drivers", New Scientist, Aug. 26, 1995, p. 19.|
|42||Klosek, S. et al., Visible light driven v-doped TiO2 photocatalyst and its photooxidation of ethanol, "J. Phys. Chem. B" 2001, 105, pp. 2815-2819.|
|43||Lettmann, C. et al., Combinatorial discovery of new photocatalysts for water purification with visible light, Angew. Chem. Int. Ed.'2001, 40, No. 17, pp. 3160-3164.|
|44||Li, X. et al., Mechanism of photodecoposition of H2O2 on TiO2 surfaces under visible light irradiation, "Langmuir" 2001, 17, pp. 4118-4122.|
|45||M. Anpo et al., "Photoluminescence and Photocatalytic Activity of Highly Dispersed Titanium Oxide Anchored onto Porous Vycor Glass", J. Phys, Chem 1985, 89, pp. 5017-5021.|
|46||M. Takahashi, "Pt-TiO2 thin films on glass substrates as efficient photocatalysts", Journal of Materials Science 24 (1989), pp. 243-246.|
|47||Meng et al.; The Effect of Substrate Temperature on the Properties of Sputtered Titanium Oxide Films, Applied Surface Science 65/66 (1993) pp. 235-239.|
|48||Morikawa, T. et al., Band-gap narrowing of titanium dioxide by nitrogen doping, "Jpn. J. Appl. Phys", vol. 40 (2001) pp. 561-563.|
|49||N. Negishi et al., "Preparation of Transparent TiO2 Thin Film Photocatalyst and Its Photocatalytic Activity", Chemistry Letters 1995, pp. 841-842.|
|50||Nakamura, I. et al., Mechanism for NO photooxidation over the oxygen-deficient TiO2 powder under visible light irradiation, "Chemistry Letters" 2000, pp. 1276-1277.|
|51||Nishikawa, T., et al., An exploratory study on effect of the isomorphic replacement of Ti4+ ions by various metal ions on the light absorption character of TiO2, "Journal of Molecular Structure (Theochem)", 545 (2001), pp. 67-74.|
|52||Nishikawa, T., et al., An exploratory study on effect of the isomorphic replacement of Ti4+ ions by various metal ions on the light absorption character of TiO2, "Journal of Molecular Structure (Theochem)", 545 (2001), pp. 67-74.|
|53||Oxide Layers Deposited from Organic Solutions, H. Schroeder in Physics of Thin Films: Advances in Research and Development, pp. 105-112, vol. 5, 1969 Academic Press.|
|54||Pierson, Hugh O., Handbook of Chemical Vapor Deposition (CVD), Noyes Publications, Park Ridge, NJ, 1992, pp. 231-237.|
|55||Robert J. Good et al. The Modern Theory of Contact Angles and the Hydrogen Bond Components of Surface Energies in Modern Approaches to Wetability, Theory and Applications, pp. 1-3, Schrader et al. Eds.|
|56||S. Sato, "Photochemical properties of Ultrathin TiO2 Films Prepared by Chemical Vapor Deposition", Journal of Photochemistry and Photobiology, A: Chemistry, 50 (1989) pp. 283-290.|
|57||S. Sitkiewitz et al., "Photocatalytic oxidation of benzene and stearic acid on sol-gel derived TiO2 thin films attached to glass", New J. Chem., 1996, 20, pp. 233-241.|
|58||Sakata, Y. et al., Generation of visible light response on the photocatalyst of a copper ion containing TiO2, "Chemistry Letters 1998", pp. 1253-1254.|
|59||T. Watanabe et al., "Photocatalytic Activity of TiO2 Thin Film Under Room Light", Photocatalytic Purification and Treatment of Water and Air, 1993, pp. 747-751.|
|60||Takeuchi, K. et al., Preparation of visible-light-responsive titanium oxide photocatalysts by plasma treatment, "Chemistry Letters 2000", pp. 1354-1355.|
|61||Takeuchi, M. et al., Photocatalytic decomposition of NO under visible light irradiation on the Cr-ion-implanted TiO2 thin film photocatalyst, "Catalysis Letters" 67 (2000) 135-137.|
|62||The Japan Times, May 21, 2002, Tuesday, Race for Technology, pp. 2-5, from LexisNexis.|
|63||TiO2 photocatalysts able to operate under visible light irradiation, "Optronics" (1997), No. 6, pp. 161-166.|
|64||U.S. Appl. No. 60/040,566, filed Mar. 14, 1997.|
|65||U.S. Appl. No. 60/305,057, filed Jul. 13, 2001.|
|66||V. Chhabra et al., "Synthesis, Characterization, and Properties of Microemulsion-Mediated Nanophase TiO2 Particles", Langmuir, vol. 11, No. 9 (1995), pp. 3307-3311.|
|67||V. Kozhukharov et al., "Sol-gel processing of titanium-containing thin coatings, Part III Properties", Journal of Materials Science 28 (1993), pp. 1283-1288.|
|68||W. Xu et al., "Preparation and Characterization of TiO2 Films by a Novel Spray Pyrolysis Method", Mat. Res. Bull., vol. 25, (1990), pp. 1385-1392.|
|69||Weinberger, B. R. et al., "Titanium Dioxide Photocatalysts Produced by Reactive Magnetron Sputtering", Appl. Phys. Lett. 66, 1995, pp. 2409-2411.|
|70||Wold; Photocatatytic Properties of TiO2, Chem. Mater., 1993, 5, pp. 280-283.|
|71||Y. Paz et al., "Photooxidative self-cleaning transparent titanium dioxide films on glass", J. Mater. Res., vol. 10, No. 11, Nov. 1995, pp. 2842-2848.|
|72||Y. Takahashi et al., "Electrical and Electrochemical Properties of TiO2 Films Grown by Organometallic Chemical Vapour Deposition", J. Chem. Soc. Faraday Trans. 1, 1982, 78, pp. 2563-2571.|
|73||Y. Takahashi et al., "Rutile Growth at the Surface of TiO2 Films Deposited by Vapour-phase Decomposition of Isopropyl Titanate", J. Chem. Soc., Faraday Trans. 1, 1985, 81, pp. 3117-3125.|
|74||Y. Takahashi, "Chemical Vapour Deposition of TiO2 Film Using an Organometallic Process and its Photoelectrochemical Behaviour", J. Chem. Soc. Faraday Trans. 1, 1981, 77, pp. 1051-1057.|
|75||Y. Takahashi, "Dip-coating of TiO2 films using a sol derived from Ti(O-i-Pr)4-diethanolamine-H2O-i-PrOH system", Journal of Materials Science 23 (1988), pp. 2259-2266.|
|76||Yamashita, Hiromi et al., Preparation of titanium oxide photocatalysts anchored on porous silica glass by a metal ion-implantation method and their photocatalytic reactivities for the degradation of 2-propanol diluted in water, "J. Phys. Chem. B" 1998, 102, 10707-10711.|
|77||Yasutaka et al., "Electrical and Electrochemical Properties of TiO2 Films Grown by Organometallic Chemical Vapor Deposition", J. Chem. Soc. Trans. 1, 1982, 78. 2563-2571.|
|78||Yoko et al.; Sol-Gel-Derived TiO2 Film Semiconductor Electrode for Photocleavage of Water, J. Electrochem Soc., vol. 138(8), Aug. 1991, pp. 2279-2284.|
|79||Yusumori et al., Preparation of TiO2 Fine Particles Supported on Silica Gel as Photocatalyst, Journal of the Ceramic Society of Japan, 102 (1994) pp. 702-707.|
|80||Zang, L. et al., Amorphous microporous titania modified with platinum(IV) chloride-a new type of hybrid photocatalyst for visible light detoxification, "J. Phys. Chem B", 1998, 102, pp. 10765-10771.|
|Citing Patent||Filing date||Publication date||Applicant||Title|
|US8012610 *||May 25, 2010||Sep 6, 2011||Ppg Industries Ohio, Inc.||Visible-light-responsive photoactive coating, coated article, and method of making same|
|US8567133||Jul 5, 2011||Oct 29, 2013||Siemens Aktiengesellschaft||Photocatalytic panel and system for recovering output products thereof|
|US9283547 *||Mar 13, 2014||Mar 15, 2016||Basf Corporation||Catalytic article with segregated washcoat and methods of making same|
|US20100233473 *||May 25, 2010||Sep 16, 2010||Ppg Industries Ohio, Inc.||Visible-light-responsive photoactive coating, coated article, and method of making same|
|US20120040193 *||Feb 4, 2010||Feb 16, 2012||Beneq Oy||Antibacterial glass|
|U.S. Classification||428/697, 428/432, 428/701, 428/426, 428/702, 428/689|
|International Classification||C03C17/34, C03C17/00, B01J37/02, C03C17/25, C03C17/245, C23C16/40, C03B18/14, B01J35/02, B01J37/34, C23C14/48, B32B9/00|
|Cooperative Classification||Y10T428/31678, Y10T428/315, C23C16/40, C03C17/2456, C03C2218/112, C03C2217/212, C03C2217/71, C03C17/3441, C03C2217/24, C03C17/25, C03C17/256, C03C2218/32, C03C2218/154, C03C2218/365, C03C17/3417, C03C17/3435, C03C2218/152, C03C2218/155, Y10T428/265, C03C17/245, C03C2218/156, Y02T50/67|
|European Classification||C03C17/25, C03C17/25C, C03C17/245, C03C17/34D4B, C03C17/34D2, C03C17/34D4D, C03C17/245C, C23C16/40|
|Feb 14, 2014||REMI||Maintenance fee reminder mailed|
|Jul 6, 2014||LAPS||Lapse for failure to pay maintenance fees|
|Aug 26, 2014||FP||Expired due to failure to pay maintenance fee|
Effective date: 20140706